Azo-dyestuffs



Patented Sept. 7, 1954 UNITED STATES PATENT OFFICE AZO -DYESTUFFSHerbert Kracker, Frankfurt (Main) -Hochst, Germany, assignor toFarbwerke Hoechst Aktiengesellschaft vormals Meister Lucius und Bruning,Frankfurt (Main)-Hochst, Germany, a

company of Germany No Drawing. Application October 10, 1951, Serial No.250,800

Claims priority, application Germany October 18, 1950 COOH X OH

NHa

wherein X and Y stand for hydrogen or any substituent, may be used withadvantage as passive components for the manufacture of valuableazo-dyestuiis. They can be combined with any active components, forinstance diazotized aniline, substituted anilines, aniline sulfonicacids, amino-phenol-sulfonic acids, aniline-carboxylic acids,amino-phenol-carboxylic acids,

napht-hylamine-sulfonic acids and the like. In this manner there areobtained azo-dyestufis of the general formula:

NHz

the following general formula:

x on i--N=N 011 wherein R1 has the meaning indicated in Fonmula II, andR2 stands for the radical of ans coupling component. If the component R2contains an amino-group capable of being diazot-ized, for instance byusing l-amino-naphtha1ene, 1- amino-E-methylbenzene,l-amino-Z-methoxy-5- methylbenzene, l-aminonaphthalene-fior -'7-sulfonic acid or the like, the disazo-dyestufi can be further diazotizedand the .diazo-compounds can be combined once more with any passivecomponent. There are thus obtained trisazo-dyestuffs of the followinggeneral formula wherein R1 has the same meaning as indicated in FormulaII, R2 stands for the radical of any coupling component containing adiazotizable amino-grou and R3 represents the radical of any couplingcomponent.

Since the new dyestuffs contain the salicylic acid grouping, they can beafter-treated on the fiber or in substance with compounds capable ofyielding metal, especially with chromium salts. The metal complexcompounds thus formed considerably improve the fastness properties ofthe dyestuffs. The orange to black dyeings, produced by theafter-treatment, are distinguished by good general fastness properties.With particular advantage the new dyestufis can be applied to the fiberdirectly in the form of their chromium complex compounds according tothe so-called meta-chrome process.

Th following examples serve to illustrate the invention, but they arenot intended to limit it thereto, the parts being by weight:

Example 1 14% parts of l-chloro-2-amino-l-hydroxybenzene are diazotizedat a temperature between 0 C. and 5 C. with 280 parts of hydrochloricacid of 24" B. and 69 parts of sodium nitrite. The diam-solution thusobtained is added to a solution of 153 parts of4-amino-2-hydroxybenzenel-carboxylic acid in parts of caustic soda and2000 parts of water. As soon as the coupling reaction is finished, thedyestufi, most of which has separated, is completely salted out. Afterdrying, it forms a deep black-brown powder and dyes wool from an acidbath dull yellow-brown shades which by after-chroming turn into deepred-brown tints of good fastness properties,

3 especially of a good fastness to washing, to fulling, to potting andto light. Dyeings of the same good properties are obtained by applyingthe dyestuif to the fiber directly as chromium parts of water,precipitated in a finely dispersed state by means of 280 parts ofhydrochloric acid of 24 B. and diazotized with 69 parts of sodiumnitrite at a temperature between 5 C. and 10 complex compound from abath containing am- 5 C. The suspension of the diazo-compound ismonium-sulfate and potassium chromate accaused to run into a solution of153 parts of 4- cording to the meta-chrome process. Thedyeamino-2-hydroxybenzene-l-carboxylic acid in stufi corresponds to thefollowing formula 125 parts of caustic soda and 500 parts of water. OH00011 When the coupling reaction is complete, th

10 mixture is acidified with 190 parts of hydrochlo- N=N OH ric acid of24 B. and completely salted out with sodium chloride. The dyestufi isobtained in 1 1 the form of a nearly black powder. It dyes wool Thefollowing dyestuffs may be obtained in a 15 similar manner;

from an acid bath claret tints which after the treatment with sodiumbichromate and sulfuric acid turn into deep brown shades with a violetDiazo Component Coupling Component Shade of the afterchrorned dyeing 1.1-amino-2-nitro-benzene 4-amino-2-hydroxybenzenel-cdarboxylic acid. o

covered orange.

6. 5-nitro-2-amino-1-hydroxydrfiirybenzene-l-carboxylic ac4-amino-3-ehloro-2-hydroxydeep red-brown.

benzene. benzene-l-carboxylio acid. 7.4.6-dich1oro-2-amino-1-hyi-amino-6-ch1oro-3-methy1- red-brown.

droxybenzene. 2-hydroxybenzene-1-carboxylic acid. 8.4-ch1oro-6-nitro-2-amino-1- d-amino-Z-hydroxybenzene- D0.

hydroxybenzene. fiilslllfofililc acid-l-carboxy cac 9.3-amino-4-hydroxy-l-methyl- 4-amino-2-hydroxybenzenereddish brown.

benzene. l-carboxylic acid. 10. 5-nitr0-2-amin0-l-hydroxydodeepdarkbrown.

benzene. 11. 4-ch1oro-5-nitro-2-amino-1- .do violet.

hydroxybenzene.

Example 2 40 hue of good general fastness properties, particu- 288 partsof 6-nitro-2-amino-1-hydroxyben zene-4-sulfonic acid of 81.2 per cent.strength are dissolved in 40 parts of caustic soda and 1000 larly of agood fastness to washing, to fulling, to rubbing, to alkalies and tolight.

The following dyestufis are obtained in a similar manner:

Dlazo-Component Shade of the after- 1. l-aminobenzene-z sulfonic4-amino-2-hydroxy-benzene medium brown.

acid. l-carboxylic acid. 2. I. -an1inobenzene-2-4-dido Do.

sulfonic acid. 3. l-aminonaphthalene 5-suldo covered brown.

nic acid. 4. 1 aminobenzene-Z-car do yellow-brown.

boxylic acid. 5. 6 chloro-2 amino-1 hy .do reddish brown.

drfirybenzene-i sulionic ac 6. 4-nitro-2-amino-l-hydroxydo Do.

benzene 6 sulfonic acid. 7. l-aminobenzene-i-sulionic 4 amino-6-methyl-2-hyyellow-brown.

acid. droxybenzene-l carboxylic acid. 8. l-aminobenzene-li-sulionickamino-B-chloro-Z-hydroxymedium brown.

acid. benzene-l-carboxylic acid. 9. l-aminonaphthalene--snl-4-amino-6-chloro-3-methylred-brown.

nic acid. 2 hydroxybenzene-l-carboxylic acid. 10.4-nitro-2-amino-1-hydroxy- 4 amino -2- hydroxy-benreddish brown.

benzene-fi-sulionic acid.

zene-6-sulionic acid-l-carboxylic acid.4-amino-2-hydroxy-benzenel-caarboxylic acid. o

medium brown.

deep red-brown.

13. 3-amino-2-hydroxy-1-medo red-brown.

th1y1lbenzene-5- sulionio ac 14. 3-amino-4-hydroxy-l-meth- -.--do Do.

benzene 5 sulfonic acid. 15. 3 amino-i-hydroxy-dido Do.

- piieinylsulfone-y-sulfonic ac 16. 6-nitro-2-amino-1-hydroxydo brownwith a violet benzene-'i-sulionic acid. hue.

aeeaers Shade of the after- Dlazo Component Coupling Component chromeddyeing 17. 4-chloro-1-amin0-benzene- 4-amino-2 hydroxy-benzencyellowishbrown.

3-su1fonic acid. l-carboxylic acid. 18. 6- chloro-3 -amino-l-meth d Do.

ylbenzenel-sulfonic acid. 19. 2 amino-4 acetylamino-l- "Dido dark brown.

hydroxy-benzene 6 sulionic acid. 20. 2 amino- 4 acetylamino-l-4-amino-3.6- dimethyl-Z-hy- Dol hydroxy-benzene- 6 suldroxybenzene-lcarboxyionic acid. lic acid. 1 21. 3 amino-4 hydroxyben- 4-amino- 3.6dichloro 2- byvery reddlshbrown.

zophenone-Z carboxylic droxybenzene-l carboxyacid. lic acid. 22. 3amino-4 hydroxyben- 4 amino 2 hydroxy -ben- Do.

%18110118-2 carboxylic zene-l-carboiylic acid. aci 23.5-nitro-2-amino-benzene-1- do red.

carboxylic acid. 24. 2-amino-5-benzoy1-aminoorange.

4 -hydroxy-diphenylsulione-3bcarboxylic acid.

Example 3 196 parts of 1-aminobenzene-4-sulfonic acid of The followingdyestuffs are obtained in a similar manner:

- Shade of the Initial Component Middle Component zi gfg after-chrom- Ped dyeing 1. l-aminobenzene-i-sulfonic acid 4-amino-2 -hydroxy-ben l 11y (1r 0 x y brown.

zene-l-carboxylic acid. 11 a p h t h a one. 2. l-aminobenzene-S-sulfonicacid. "do. 2 11 y d! 0 xy y e 1 l o w i s h naphthabrown.

ene. 3. l-aminobenzene-2-sulfonic acid .do 1.5-dihydroxdark brown.

ynaphthalene. 4. l-aminobenzene-i-sulfonic acid do 1 h y d to xy brown.

11 a p h t h a lene-4-su1- ionic acid. 6. l-aminonaphthaleneA-sulfonicacid -do 1 .3-d1hydrox- Do.

ybenzene. 6. 1-aminobenzene-2.5-disulfonic acid do 1 11 y dr 0 xy- Do.

- n-a p h t h a lene.

88.4 per cent. strength are diazotlzed with 280 Example 4 parts ofhydrochloric acid of 24 B. and 69 parts of sodium nitrite, and thediazo-solution is then combined with a solution of 153 parts ofl-ami-no- 2-hydroxybenzene-l-earboxylic acid in 165 parts of causticsoda and 500 parts of water with formation of the dyestuff. The solutionof the dyestuff is clarified, mixed with 69 parts of sodium nitrite andthe mixture is then caused to run at 0 C. into 375 parts of hydrochloricacid of 24 B. The clear diazo-solution is then caused to run into asolution of 1'74 parts of 1-phenyl-3- methyl-S-pyrazolone in 165 partsof caustic soda and 500 parts of water. When the formation of thedyestuff is complete, the mixture is acidified with 190 parts ofhydrochloric acid of 24 B. and the dyestuii is completely salted outwith sodium chloride. It is a brown powder and dyes wool from an acidbath yellow-brown tints which by after-chroming turn into full brownshades of good general fastness properties, particularly of goodfastness to decatizing, to carbonizing, to alkalies and to light. Thedyestufi corresponds to the following formula COOH HOsSON=N on Thediazo-solution of the diazotized dyestuff from diazotized1-aminobenzene-4-sulfonic acid and 4-amino-2 hydroxybenzene 1 carboxylicacid obtained as described in Example 3 is combined in hydrochloric acidsolution with 143 parts of l-aminonaphthalene, the disazo-dyestufl thusobtained is diazotized again with 69 parts of sodium nitrite and thediazo-solution is then coupled in a caustic alkaline solution with 144parts of 2-hydroxynaphthalene. The trisazo-dyestuff is obtained in theform of a deep dark-brown powder. It dyes wool from an acid bath andthen after-chromed full red-brown tints which are distinguished by goodfastness properties, especially by a good fastness to washing, todecatizing, to alkalies and to light. The dyestuff corresponds to thefollowing formula COOH HOzS-O-N: OH

Similar dyestufis are obtained by using, instead ofl-aminobenzenei-sulfonic acid, other aniline-sulfonic acids,chloraniline-sulfonic acids, chloro-toluidine-sulfonic acids,nitraniline-sulfonic acids, naphthylamine-sulfonic acids or the like,instead of l-aminonaphthalene, for instance3-amino-4-methoxy-1-methylbenzene, 1-amino-3-methylbenzene, 1-amino-2.5-dimethylbenzene, l-amino 2.5 dimethoxybenzene, l-amino 2.5diethoxybenzene, 1 aminonaphthalene-6- or -'7-sulfonic acid or the like,and instead of 2-hydroxynaphthalene, for instance l-hydroxynaphthalene,l-hydroxynaphthalene-4- or -5-sulfonic acid,2-hydroxynaphthalene-G-sulfonic acid, l-hydroxynaphthalene-3.6-disulfonic acid, 2-hydroxynaphthalene-3.6- disulfonic acid,1-phenyl-3-methy1-5-pyrazolone, 1.3-dihydroxybenzene and others.

I claim:

1. The azo-dyestuffs corresponding to the following general formula XCOOH wherein R1 is a radical selected from the group which consists ofradicals of the benzene and naphthalene series, and X and Y eachrepresent a substituent selected from the group which consists ofhydrogen, methyl and chlorine.

2. The azo-dyestufis corresponding to the following general formula COOHwherein R1 is a radical selected from the group which consists ofradicals of the benzene and naphthalene series containing at least onegroup imparting solubility in water.

8 3. The azo-dyestufi corresponding to the following formula NO: OH COOH4. The azo-dyestufl corresponding to the following formula COOH HOs OHNH! 5. The azo-dyestufi corresponding to the following formula OH COOHSOsH NHa 6. The azo-dyestufi corresponding to the following formula COOHCOOH References Cited in the file of this patent UNITED STATES PATENTSName Date Mettler Oct. 19, 1915 Ostertag Mar. 8, 1932 Number

1. THE AZO-DYESTUFFS CORRESPONDING TO THE FOLLOWING GENERAL FORMULA